JPH10237174A - Silylated polymethylsilsesquioxane - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject compound having crosslinking ability with a matrix polymer when used as an additive to the polymer and useful as a resist material, etc., by adding functional groups to a polymethylsilsesquioxane. SOLUTION: This silylated polymethylsilsesquioxane expressed by formula II [(k) is a positive number less than (m), an amount of residual silanol residues (m-k)/(m+n)<=0.12; R<1> to R<3> are each H or a (substituted) monovalent hydrocarbon] is obtained by silylating silanol groups in a polymethylsilsesquioxane expressed by formula I [(m) and (n) are positive number giving molecular weights.) and having 380-2000 polystyrene-reduced number average molecular weight (Mn) with a silyl group-containing compound having a crosslinkable carbon-carbon double bond. In (m) and (n) of formula I, m/(m+n) value lies in a A domain, the A domain is surrounded by each of straight lines expressed by m/(m+n)=0.152×Mn×10<-3> +0.10, 1/(Mn×10<-3> =1000/2000, 1/(Mn×10<-3> )=1000/380, m/(m+n)=0.034/(Mn×10<-3> ) in a graph expressed by 1/(Mn×10<-3> ) x-axis and m/(m+n) y-axis and contains each straight line and each cross point of the straight lines.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a polymethylsilsesquioxane having a reactive group, a method for producing the same, and a curable composition using the same.

[0002]

2. Description of the Related Art Polymethylsilsesquioxane is a general term for silicone resins having a ratio of the number of oxygen atoms to the number of silicon atoms of 1.5. Heat resistance, electrical insulation,
It has excellent flame resistance, etc. and is used as a resist material, an interlayer insulating film, etc. during semiconductor manufacturing [see "Silicone Handbook" edited by Kunio Ito, Nikkan Kogyo Shimbun (1990), etc.]

As a method for synthesizing polymethylsilsesquioxane, methyltrichlorosilane is mixed with a ketone and an ether in the presence of an amine or dissolved in a single solvent, and water is added dropwise thereto for hydrolysis, followed by heat condensation. Method for synthesis [Japanese Patent Publication No. 60-17214, Japanese Patent Publication No. 1-43
773, U.S. Pat. No. 4,399,266], trifunctional methylsilane is dissolved in an organic solvent.
To -50°C under a pressure of an inert gas of 1000 to 3000 Pa, water is added dropwise to hydrolyze, followed by heat condensation to synthesize [see Japanese Patent Publication No. 62-16212, EP 0406911 A1], organic solvent. In which methyltriacetoxysilane and an equivalent amount thereof are reacted with alcohol and/or water to synthesize an alkoxyacetoxysilane, which is polycondensed in the presence of sodium hydrogen carbonate in an organic solvent to obtain a prepolymer, Furthermore, the prepolymer is heated and condensed in the presence of at least one catalyst selected from alkali metal hydroxides, alkaline earth metal hydroxides, alkali metal fluorides, alkaline earth metal fluorides and triethylamine. Method of synthesis [JP-A-3-
20331 gazette], and an alkali metal carboxylate and a lower alcohol are dissolved in a mixed solution forming two layers of water and a hydrocarbon solvent, and methyltrihalosilane is added dropwise thereto to hydrolyze and heat-condensate the mixture. A method of synthesizing [see JP-A-3-227321] is known.

A characteristic of the polymethylsilsesquioxanes obtained by these methods is that they are commonly hard but brittle. Some of these have been devised to solve this drawback, and in Japanese Patent Publication No. 1-43773,
15-30% (weight) of polymethylsilsesquioxane
, But gel permeation chromatography (GP
Although it is adjusted so as to be occupied by a portion having a standard polystyrene equivalent molecular weight of 20,000 or less according to C), it is still 1.
Only a coating film having a thickness of about 8 to 2.0 μm can be produced, and EP 0406911A1 has a maximum thickness of 3 to 3.5 μm.
The coating film of 1 is obtained without cracks. A thicker film than this causes cracks, and much less flexibility to obtain an independent film.

As disclosed in Japanese Patent Application No. 7-208087 and Japanese Patent Application No. 7-208143, the inventors of the present invention have a specific molecular weight range and a hydroxyl group content range, and preferably polymethylsilsesqui produced by a specific method. It was found that by curing oxane, a film having both flexibility and high thermal stability can be obtained.

Silylation of residual silanols of polysilsesquioxane is described in J. Am. Chem. Soc., 1990, 112, 1931-19.
36 and the like disclose a synthetic method. JP 61-221
No. 232 discloses the above Japanese Patent Publication No. 62-16212.
EP No. 0406911A1 describes a method of synthesizing polysilsesquioxane to obtain a silylated polysilsesquioxane by stopping the reaction with a silylating agent. JP-A-6-279586, JP-A-6-287
No. 307 and JP-A No. 7-70321, 50 to 99.9 mol% of the side chain organic groups are methyl groups, and the remaining hydroxyl groups of polysilsesquioxane containing a crosslinkable reactive group are added to the organic groups. It is described that trimethylsilylation stabilizes without gelation. However, the polymethylsilsesquioxane disclosed by the inventors in Japanese Patent Application Nos. 7-208087 and 7-208143 is It can be stably stored at room temperature without silylation or gelation during production. JP-A-5-125187 discloses that by trialkylsilylating a hydroxyl group of a polysilsesquioxane having a number average molecular weight of 100,000 or more and 50 to 100 mol% of side chain organic groups are methyl groups, It is described to enhance storage stability. The above Japanese Patent Publication No. 62-16212 also describes that stability is increased by silylating the hydroxyl groups of polymethylsilsesquioxane.

In addition to the above, silsesquioxanes having various crosslinkable reactive groups as organic groups of silsesquioxane are described in documents such as Chem. Rev. 1995, 95, 1409-1430.

[0008]

DISCLOSURE OF THE INVENTION Problems to be Solved by the Invention
The polymethylsilsesquioxane disclosed in 208087 and Japanese Patent Application No. 7-208143 has many silanol groups and is excellent in storage stability. The cured product has flexibility that was difficult to achieve with the conventional cured product of polymethylsilsesquioxane, and has extremely high thermal stability. High thermal stability can also be explained by the fact that the crosslink density after curing becomes high for some reason, but this and the flexibility of the cured film are contradictory properties, and having these properties together This is a unique feature of polymethylsilsesquioxane. The present invention, by imparting a functional group to the polymethylsilsesquioxane having such characteristics, has functionality (additive to polymer, crosslinkability with matrix polymer when used as a filler, or It is an object of the present invention to provide a method for allowing curing by polyaddition or addition polymerization of polymethylsilsesquioxane).

[0009]

[M and n are positive numbers giving the above-mentioned molecular weight, and the value of m/(m+n) is in the area A in FIG. 1. The region A is surrounded by each straight line represented by the following equations 1 to 4 in the graph of FIG. 1 in which the horizontal axis is 1/(Mn×10 ⁻³ ) and the vertical axis is m/(m+n). This is a region that is included in each line and includes the intersection of each line. (Formula 1): m/(m+n)=0.152/(Mn×10 ⁻³ )+0.10 (Formula 2): 1/(Mn×10 ⁻³ )=1000/2000 (Formula 3): 1/ (Mn×10 ⁻³ )=1000/380 (Formula 4): m/(m+n)=0.034/(Mn×10 ⁻³ )]

Of the formula [CH ₃ SiO _3/2 ] _n [CH ₃ Si(OH)O _2/2 ] for silylating silanol groups of polymethylsilsesquioxane.
_mk [CH ₃ Si(OSiR ¹ R ² R ³ )O _2/2 ] _k [In the above formula, k is a positive number smaller than m,
The amount of residual silanol groups represented by (m−k)/(m+n) is 0.12 or less, and R ¹ , R ² and R ³ are substituted or unsubstituted monovalent hydrocarbon groups, one of which is The above is a group having a crosslinkable carbon-carbon double bond] a method for producing a silylated polymethylsilsesquioxane,
A silylated polymethylsilsesquioxane that can be produced in this manner and a composition consisting essentially of this silylated polymethylsilsesquioxane and a polyorganosiloxane reactive therewith.

The polymethylsilsesquioxane used in the present invention has a polystyrene reduced number average molecular weight (Mn) of 38.
In the range of 0 to 2000 and having the formula [CH ₃ SiO _3/2 ] _n [CH ₃ Si(OH)O _2/2 ].
_m [m, n is a positive number giving the above molecular weight, m/(m+
The value of n) is in the area A of FIG. The region A is surrounded by each straight line represented by the following equations 1 to 4 in the graph of FIG. 1 in which the horizontal axis is 1/(Mn×10 ⁻³ ) and the vertical axis is m/(m+n). This is a region that is included in each line and includes the intersection of each line. (Formula 1): m/(m+n)=0.034/(Mn×10
^-3 )+0.25 (Formula 2): 1/(Mn×10 ⁻³ )=1000/2000 (Formula 3): 1/(Mn×10 ⁻³ )=1000/380 (Formula 4): m/( m+n)=0.034/(Mn×10
^-3 )]]. The polymethylsilsesquioxane preferably contains an oxygen-containing organic solvent and, on the other hand, 50%
A methyltrihalosilane represented by the formula: MeSiX ₃ (Me is a methyl group, X is a halogen atom) in a two-phase system of water and an organic solvent containing or not containing a hydrocarbon solvent in an amount of less than or equal to volume%. It is produced by condensing hydrolysis and its hydrolysis product. If this production method is not used, the flexibility and heat resistance of the film of the cured product of this polymethylsilsesquioxane will be reduced even if the molecular weight and silanol group content are within the above ranges. That is, as described above, it does not become a characteristic polymethylsilsesquioxane.

The following examples can be given as preferable synthesis methods of polymethylsilsesquioxane having the above-mentioned molecular weight range and hydroxyl group content. (1) Forming a two-phase system of an oxygen-containing organic solvent containing or not containing 50% by volume or less of a hydrocarbon solvent and water (dissolving a water-soluble inorganic base or a salt of a weak acid having a buffering capacity, if necessary) The methyltrihalosilane represented by the formula MeSiX ₃ (Me is a methyl group and X is a halogen atom) or an oxygen-containing organic solvent containing or not containing 50% by volume or less of a hydrocarbon solvent is added with the methyltrihalosilane. A method in which a dissolved solution is added dropwise and hydrolyzed to condense the hydrolysis product. (2) A method in which a solution in which methyltrihalosilane is dissolved in oxygen-containing water containing 50% by volume or less of the above hydrocarbon solvent is added dropwise only to water, resulting in a two-phase system reaction. Otherwise, perform the same as (1). (3) A solution of methyltrihalosilane dissolved in oxygen containing 50% by volume or less of a hydrocarbon solvent and water are simultaneously added dropwise to an empty reaction vessel so that a two-phase system reaction results. How to do. Otherwise, perform the same as (1).

Here, X is preferably bromine or chlorine, more preferably chlorine. The fact that water and the organic solvent form two phases means that the water and the organic solvent are immiscible and do not form a uniform solution. By slowing the stirring speed, the organic layer and the aqueous layer maintain the layered state. Alternatively, the mixture may be vigorously stirred into a suspension state. Hereinafter, the former is referred to as “forming two layers”.

The organic solvent used in this production method may dissolve methyltrihalosilane and may be dissolved in water to some extent, but an oxygen-containing organic solvent capable of forming two phases with water is used, and further 50% by volume. The following hydrocarbon solvents may be included. If the content of the hydrocarbon solvent is higher than this, the amount of gel produced increases, the yield of the target product decreases, and it becomes impractical. As this organic solvent, even if it is a solvent which can be freely dissolved in water, a solvent which is not miscible with the aqueous solution of a water-soluble inorganic base or a salt of a weak acid having a buffering capacity can be used.

Examples of the oxygen-containing organic solvent include ketone solvents such as methyl ethyl ketone, diethyl ketone, methyl isobutyl ketone, acetylacetone and cyclohexanone, ether solvents such as diethyl ether, dinormal propyl ether, dioxane, diethylene glycol dimethyl ether and tetrahydrofuran, ethyl acetate. , Ester solvents such as butyl acetate and butyl propionate, alcohol solvents such as n-butanol and hexanol, but not limited to these, and ketones, ethers, and alcohol solvents are more preferable. You may use these solvents in mixture of 2 or more types. Examples of the hydrocarbon solvent include aromatic hydrocarbon solvents such as benzene, toluene and xylene, aliphatic hydrocarbon solvents such as hexane and heptane, halogenated hydrocarbon solvents such as chloroform, trichloroethylene and carbon tetrachloride. It is not limited to these. The amount of the organic solvent used is not particularly limited, but is preferably in the range of 50 to 2000 parts by weight with respect to 100 parts by weight of methyltrihalosilane. If the organic solvent is less than 50 parts by weight with respect to 100 parts by weight of methyltrihalosilane, it will be insufficient to dissolve the generated polymethylsilsesquioxane, and in some cases, the molecular weight of the target may be increased to increase the molecular weight. If polymethylsilsesquioxane in the range is not obtained, and if it exceeds 2000 parts by weight, hydrolysis and condensation of methyltrihalosilane do not proceed rapidly and polymethylsilsesquioxane in the target molecular weight range cannot be obtained. Because. The amount of water used is not particularly limited, but is preferably 10 to 3000 with respect to 100 parts by weight of methyltrihalosilane.
The range is parts by weight.

The reaction can be carried out by using water to which nothing is added to the aqueous phase, but the molecular weight of the polymethylsilsesquioxane produced is high. This is because hydrogen chloride generated from chlorosilane accelerates the reaction. Therefore, by adding a water-soluble inorganic base that suppresses acidity or a salt of a weak acid that has a buffering capacity, polymethylsilsesquioxyl having a lower molecular weight is added. Can synthesize sun.

Examples of the water-soluble inorganic bases include water-soluble alkalis such as lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide and magnesium hydroxide, and sodium carbonate is used as a weak acid salt having a buffering capacity. , Carbonates such as potassium carbonate, calcium carbonate, magnesium carbonate, hydrogencarbonates such as sodium hydrogencarbonate, potassium hydrogencarbonate, oxalates such as potassium bis(oxalate) trihydrogen, potassium hydrogen phthalate, sodium acetate, etc. Examples thereof include, but are not limited to, carboxylates, phosphates such as disodium hydrogen phosphate and potassium dihydrogen phosphate, and borates such as sodium tetraborate. The amount of these used is preferably 1.8 gram equivalent or less with respect to 1 mol of halogen atom in one molecule of trihalosilane. That is, the amount is preferably 1.8 times or less as much as the amount for neutralizing the hydrogen halide produced when the halosilane is completely hydrolyzed. If it is more than this, an insoluble gel is likely to be formed. Two or more kinds of these water-soluble inorganic bases or salts of weak acids having a buffering capacity may be mixed and used within the above quantitative range.

In the hydrolysis of methyltrihalosilane, the stirring speed of the reaction solution may be slow enough to hold two layers of the aqueous phase and the organic solvent, or may be stirred vigorously to form a suspension. It doesn't matter. The reaction temperature is appropriately in the range of room temperature (20°C) to 120°C,
It is preferably about 100°C.

The polymethylsilsesquioxane of the present invention contains a unit having a lower alkyl group other than a methyl group or a monofunctional (R ₃ SiO _1/2) due to impurities contained in the raw material. ), bifunctional (R ₂ SiO _2/2 ), 4
Some functional (SiO _4/2 ) units may be included. Further, the polymethylsilsesquioxane contains an OH group and its structure is as shown in the above structural formula.
Units with H groups may be present. The polymethylsilsesquioxane of the present invention essentially has a structure satisfying the above-mentioned conditions. However, regarding the structural unit generated due to the causes as described above, the polymethylsilsesquioxane is They may be present as long as they do not impair the characteristic properties of.

R ^{1 to} R ³ of the silyl group for silylating the hydroxyl group of polymethylsilsesquioxane are substituted or unsubstituted monovalent hydrocarbon groups, at least one of which is a crosslinkable carbon-carbon double bond. It includes a bond. Crosslinkable carbon-
Examples of the group containing a carbon double bond include a vinyl group, a (meth)acryloyl group and an alkenyl group. Examples of the remaining non-reactive group include an alkyl group such as a methyl group, an ethyl group and a propyl group, an aryl group such as a phenyl group, and halogen-substituted organic groups thereof.

As the silylation method of the hydroxyl group of polymethylsilsesquioxane with a silyl group having a reactive substituent, any method of reacting with the above R ^{1 to} R ³ trisubstituted halosilane, N,N- Diethylaminosilane, N-
Examples include silylacetamide, a method using a nitrogen-containing silylating agent such as hexasubstituted disilazane, a method of reacting with a trisubstituted silanol, and a method of reacting with a hexasubstituted disiloxane under weak acidity. When a halosilane is used, a hydrogen halide produced as a by-product may be neutralized in the presence of a base. When using a nitrogen-containing silylating agent, a catalyst such as trimethylchlorosilane or ammonium sulfate may be added. The silylation reaction can be carried out in a solvent, but the solvent can be omitted. Suitable solvents include aromatic hydrocarbon solvents such as benzene, toluene and xylene, aliphatic hydrocarbon solvents such as hexane and heptane, ether solvents such as diethyl ether and tetrahydrofuran, ketone solvents such as acetone and methyl ethyl ketone, acetic acid. Examples thereof include ester solvents such as ethyl and butyl acetate, halogenated hydrocarbon solvents such as chloroform, trichloroethylene and carbon tetrachloride, and dimethylformamide and dimethylsulfoxide.

The temperature of this silylation reaction is suitably 0 to 200°C, preferably 0 to 140°C.

The silylated polymethylsilsesquioxane obtained as described above can form a composition with good compatibility with a certain polyorganosiloxane, and can be further reacted by reacting in the presence of a curing catalyst. A cured product having various physical properties can be obtained. Examples of this polyorganosiloxane include, but are not limited to:

(I) Organopolysiloxane having alkenyl group General formula: R ⁴ _a R ⁵ _b SiO _(4-ab)/2 (wherein R ^{4 a}
Is an alkenyl group, R ⁵ is an alkyl group having 1 to 3 carbon atoms, a is the number necessary for at least 2 R ^{4 to} be present in one molecule, and 1.8≦a+b≦ 2.
The viscosity at a temperature of 25° C.
An organopolysiloxane having a content of 0 cp to 100,000 cp. The viscosity is preferably 100 cp to 50,000 cp, more preferably 300 cp to 10,000 cp. Some examples are as follows.

[0024]

[Chemical 1]

(Ii) Organohydrogenpolysiloxane General formula: R ⁶ _a H _b SiO _(4-ab)/2 (wherein R ⁶ is an alkyl group having 1 to 3 carbon atoms, and b is 1 molecule) The number of hydrogen atoms required to exist at least 3 or more in the above, 1.8≦a+b≦2.3) and the viscosity at a temperature of 25° C. is 1 cp to 100,000 cp. Hydrogen polysiloxane. The viscosity is preferably 100 cp to 50,000 cp, more preferably 10 cp.
Those of 00 cp to 10,000 cp are used. Some examples are as follows.

[0026]

[Chemical 2]

Further, dimethylpolysiloxane and polysiloxane having a phenyl group can be exemplified. These polyorganosiloxanes may be copolymers with polyalkylene oxides such as polyethylene oxide and polypropylene oxide, etc., as long as they satisfy the condition that the above compatibility is also good, and they may be tetrafunctional units or trifunctional units. It may contain a functional unit.

The composition of the present invention is preferably a curable composition containing the following components and: Component Silylated polymethylsilsesquioxane component according to claim 1, claim 2 or claim 3 Polysiloxane compound having an average of two or more hydrogen atoms directly bonded to Si atoms in one molecule Component Curing catalyst

The curable composition may further contain the following components. Ingredients Crosslinkable carbon-carbon double bonds average 2 per molecule.
Organopolysiloxane with more than one

This curable composition contains a component reactive with the component and a curing catalyst, but may further contain an organopolysiloxane as a component depending on the purpose. The component organohydrogenpolysiloxane is not particularly limited as long as it reacts with at least the component to obtain a curable composition. Specific examples thereof include linear organohydrogenpolysiloxane, branched organohydrogenpolysiloxane, hydridodimethylsilylated polymethylsilsesquioxane, and silicone resin having a hydrosilyl group.

When the viscosity of the polyorganosiloxane is low, the composition containing the silylated polymethylsilsesquioxane and the polyorganosiloxane can be prepared by simply mixing the two when the viscosity of the polyorganosiloxane is high. Can be obtained by a kneading and blending method using a kneader, and by dissolving both components in an organic solvent. The organic solvent is not particularly limited as long as it can dissolve both components uniformly, and the above-mentioned aromatic hydrocarbon solvent, aliphatic hydrocarbon solvent, halogenated hydrocarbon solvent, ketone solvent, ether solvent. , Ester solvents and the like.

[0032]

EXAMPLES The present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples.

Reference Example 1 A reaction vessel equipped with a reflux condenser, a dropping funnel, and a stirrer was charged with 63.5 sodium carbonate.
g (0.60 mol) and 400 ml of water were added and stirred, and 400 ml of methyl isobutyl ketone was added thereto. The stirring speed was low enough to keep the organic layer and the aqueous layer. Then, 74.7 g (0.5 mol) of methyltrichlorosilane
Was slowly dropped from the dropping funnel. At this time, the temperature of the reaction mixture rose to 50°C. Further, the reaction mixture was heated and stirred for 24 hours on an oil bath at 60°C. After the reaction,
The organic layer was washed until the washing water became neutral, and then the organic layer was dried using a desiccant. After removing the desiccant, the solvent was distilled off under reduced pressure and vacuum drying was performed overnight to obtain polymethylsilsesquioxane as a white solid. The molecular weight distribution of this polymethylsilsesquioxane was measured by GPC [HLC-8020 manufactured by Tosoh Corporation, and the column is TSKgelG manufactured by Tosoh Corporation].
Two MH _HR -L (trademarks) were used and chloroform was used as a solvent], and the weight average molecular weight in terms of standard polystyrene was 3270, and the number average molecular weight was 920. The amount of hydroxyl groups determined from ²⁹ Si NMR spectrum [measured by ACP-300 manufactured by Bruker] was 0.22 per silicon atom [this value is m/
Corresponding to (m+n)].

Reference Example 2 Using the same reactor as in Reference Example 1, 2 L of water and 1.5 L of methyl isobutyl ketone were vigorously stirred so as not to form two layers, and methyl was dissolved in 0.5 L of methyl isobutyl ketone. Trichlorosilane 74
5 g (5.0 mol) was slowly added dropwise so that the temperature of the reaction mixture did not exceed 50°C. Further, the reaction mixture was heated and stirred on an oil bath at 50° C. for 2 hours and treated in the same manner as in Reference Example 1 to obtain polymethylsilsesquioxane as a white solid. When the molecular weight distribution of the polymethylsilsesquioxane thus obtained was analyzed by the same method as in Reference Example 1, the weight average molecular weight was 9180 and the number average molecular weight was 1060. The amount of hydroxyl groups is 1
The number was 0.22 per atom.

Example 1 The inside of a reaction vessel equipped with a reflux condenser, a dropping funnel, and a stirrer was replaced with argon, and 3.0 g of polymethylsilsesquioxane of Reference Example 1 was added,
It was dissolved in 9 mL of methyl isobutyl ketone, and 1.47 g of triethylamine was added. 1.83 g of vinyldimethylchlorosilane was added dropwise with stirring for 1 minute, and the mixture was reacted at room temperature for 2 hours. After the reaction was stopped by adding water, the organic layer was washed until the washing water became neutral, and then the organic layer was dried using a desiccant. After removing the desiccant, the solvent was distilled off under reduced pressure and vacuum drying was carried out for 2 days and night to obtain 2.37 g of vinyldimethylsilylated polymethylsilsesquioxane as an extremely slightly fluid solid. ²⁹ SiNMR
The amount of residual hydroxyl groups obtained from the spectrum was 0.06 per silicon atom belonging to the silsesquioxane skeleton [this value corresponds to (m-1)/(m+n)].

0.88 g of this vinyldimethylsilylated polymethylsilsesquioxane and vinyl groups at both ends (weight content of vinyl group 0.12 wt %, viscosity 9000 cS
t) Using 3.5 g of polydimethylsiloxane (weight ratio 2
0:80), these were dissolved in 4.4 g of toluene and sufficiently stirred, and then platinum-divinyltetramethyldisiloxane complex was added to the vinyl group in an amount of platinum atom of 200 ppm,
2-methyl-3-butyn-2-ol 0.00028
g, the following formula

[0037]

[Chemical 3]

After adding 0.21 g of the crosslinking agent represented by the formula (1) and removing the solvent, the mixture was heated and cured at 100° C. for 12 hours to obtain a silicone rubber film containing polymethylsilsesquioxane. The film had good transparency and showed good compatibility between silylated polymethylsilsesquioxane and polydimethylsiloxane.

Example 2 A reactor similar to that of Example 1 was used.
Used, 70 g of polymethylsilsesquioxane of Reference Example 2
Was dissolved in 210 mL of methyl isobutyl ketone. Ami
Was not used. Vinyl dimethyl chloride on an ice bath
41.0 g of orchid was added dropwise over 3 minutes and reacted at room temperature for 1 hour.
And post-treating it in the same manner as in Example 1
71.6 g of polymethyl silsesquioxane
Obtained as a slightly fluid solid. ²⁹Si NMR spectrum
The amount of residual hydroxyl group obtained from the
0.05 per silicon atom belonging to the skeleton
It was

This vinyldimethylsilylated polymethylsilsesquioxane and the same polydimethylsiloxane having vinyl groups at both ends as in Example 1 were cured in the same manner as in Example 1 using a weight ratio of 20:80. Thus, a uniform silicone rubber film containing polydimethylsiloxane was obtained.

The tensile test of this film was conducted according to JIS K 6
According to No. 301, the stress-strain curve does not show yield, the 10% elastic modulus (the value obtained by dividing the stress when the strain is 10% by the strain) is 1.3 MPa, and the silylated polymethylsilsesqui Since the value without oxane was 0.5 MPa, the reinforcing effect was observed.

A dynamic property test was conducted according to JIS K 6394. The shear modulus at a test temperature of 20° C. and a test frequency of 1 Hz was 33 with a film containing vinyldimethylsilylated polymethylsilsesquioxane.
2.5 MPa compared to the value of 13 MPa without vinyldimethylsilylated polymethylsilsesquioxane.
Doubled.

Example 3 The same vinyldimethylsilylated polymethylsilsesquioxane used in Example 2 and the same polydimethylsiloxane having vinyl groups at both ends as used in Example 1 were used in a weight ratio. It was used at 40:60 and cured in the same manner as in Example 1 to obtain a silicone rubber film containing polymethylsilsesquioxane and having good transparency. When the tensile test of this film was conducted in the same manner as in Example 2, the 10% elastic modulus was 8.0 MPa, which was 16% as compared with the case where no silylated polymethylsilsesquioxane was contained.
This is 6 times the value when silsesquioxane and polydimethylsiloxane were used at a weight ratio of 20:80, and the reinforcing effect was further enhanced.

When a dynamic property test was conducted in the same manner as in Example 2, the shear modulus at a test temperature of 20° C. and a test frequency of 1 Hz was a film containing vinyldimethylsilylated polymethylsilsesquioxane. The pressure was 82 MPa, and as in the case of the tensile test, a higher reinforcing effect was observed.

Example 4 1.75 g of the same vinyldimethylsilylated polymethylsilsesquioxane used in Example 2 and 0.38 of the same crosslinking agent used in Example 1
g was dissolved in 1.8 g of toluene, and the platinum-divinyltetramethyldisiloxane complex was added with 200 ppm of platinum atom based on the vinyl group and 0.00042 g of 2-methyl-3-butyn-2-ol. 12 hours at ℃, 13
It was heated and cured at 0° C. for 2 hours to obtain a polymethylsilsesquioxane cured product film. When this film was subjected to a dynamic viscoelasticity test in a tensile mode, a test temperature of 20
The storage elastic modulus at 0°C and a test frequency of 1 Hz was 0.9 to 1.0 GPa. This cured film is disclosed by the inventors in Japanese Patent Application Nos. 7-208087 and 7-20814.
When a bending test was performed using a bending tester of JIS K-5400 on an independent film as flexible as a cured product of silanol condensation of polymethylsilsesquioxane disclosed in No. 3 and having a thickness of 200 μm, a diameter of 10 mm was obtained. The film did not break even if it was bent by 180° using the mandrel, and no crack was generated.

Reference Example 3 Using the same reactor as in Example 1, polymethylsilsesquioxane 10.
Dissolve 8 g in 30 mL of methyl isobutyl ketone and add 5.02 g of dimethylchlorosilane to 1 while stirring on an ice bath.
The mixture was added dropwise for 5 minutes and reacted at room temperature for 2 hours. After the reaction was stopped by adding water, the organic layer was washed until the washing water became neutral, and then the organic layer was dried using a desiccant. After removing the desiccant, the solvent was distilled off under reduced pressure and vacuum drying was carried out for 2 days and night to obtain 11.3 g of hydridodimethylsilylated polymethylsilsesquioxane as a highly viscous liquid. ²⁹ SiN
The amount of residual hydroxyl groups determined from the MR spectrum was 0.05 per silicon atom belonging to the silsesquioxane skeleton.

(Example 5) In the same manner as in Example 4, 1.70 g of vinyldimethylsilylated polymethylsilsesquioxane of Example 2 and 1.70 g of hydridodimethylsilylated polymethylsilsesquioxane of Reference Example 3 were used. Using 56 g, platinum-divinyltetramethyldisiloxane complex and 2-methyl-3-butyn-2-ol were added in the same ratio as in Example 4, and heated in the same manner to give a polymethylsilsesquioxane cured product film. Obtained. When a dynamic viscoelasticity test was conducted in the same manner as in Example 4, the storage elastic modulus at a test temperature of 20° C. and a test frequency of 1 Hz was 2 GPa. This cured film is also disclosed by the inventors in Japanese Patent Application Nos. 7-208087 and 2081.
A flexible film, which is as flexible as a cured product obtained by silanol condensation of polymethylsilsesquioxane disclosed in No. 43, and has a thickness of 90 μm was subjected to a bending test using a bending tester of JIS K-5400, and the diameter was 2 mm. The film did not break even if it was bent by 180° using the mandrel, and no crack was generated.

Comparative Example 1 The non-silylated polymethylsilsesquioxane of Reference Example 2 and the same polydimethylsiloxane having vinyl groups at both ends as used in Example 1 were used in a weight ratio of 20:80 and weight. Used in a ratio of 40:60,
Attempting to obtain a silicone rubber film containing polymethylsilsesquioxane by curing in the same manner as in Example 1,
It did not disperse as readily as vinyldimethylsilylated polymethylsilsesquioxane. The obtained cured product blend film was opaque and could not be used for measurement of mechanical properties.

Reference Example 4 Using the same reactor as in Example 1, 70 g of polymethylsilsesquioxane of Reference Example 2 was used.
Was dissolved in 210 mL of methyl isobutyl ketone, and 35.4 g of triethylamine was added. 38.3 g of trimethylchlorosilane was added dropwise over 17 minutes, reacted at room temperature for 2 hours, and post-treated in the same manner as in Example 1 to obtain 72.1 g of trimethylsilylated polymethylsilsesquioxane as a white solid. The amount of residual hydroxyl groups determined from the ²⁹ Si NMR spectrum was 0.06 per silicon atom belonging to the silsesquioxane skeleton.

Comparative Example 2 The trimethylsilylated polymethylsilsesquioxane of Reference Example 4 and the same polydimethylsiloxane having vinyl groups at both ends as used in Example 1 were used in a weight ratio of 20:80 and a weight ratio of 40. : Used in 60,
Curing was carried out in the same manner as in Example 1 to obtain two types of silicone rubber films containing polymethylsilsesquioxane. These films had good transparency and showed good compatibility of silylated polymethylsilsesquioxane with polydimethylsiloxane. When a tensile test of these films was conducted in the same manner as in Example 2, the weight ratio of silylated polymethylsilsesquioxane to polydimethylsiloxane was 2
The 10% elastic modulus of the film made at 0:80 is 1.0
MPa (breaking elongation 190%), and the value in Example 2 was 1.
The value was close to 3 MPa (elongation at break 190%). However, while the test piece of Example 2 was transparent until it broke, the test piece containing the trimethylsilylated silsesquioxane of this comparative example had a practical problem of whitening when the strain exceeded 50%. Occurred. Furthermore, when the weight ratio of trimethylsilylated silsesquioxane and polydimethylsiloxane was set to 40:60, the 10% elastic modulus was 0.5MP.
a and the weight ratio of 20:80, which is lower than that in the case of containing no silylated polymethylsilsesquioxane.
Same as 5MPa, that is, no reinforcing effect is seen. In Example 3, this value is 8.0 MPa. This is because there is no cross-linking between the trimethylsilylated silsesquioxane and polymethylsilsesquioxane of this comparative example, so a small amount of the filling effect was observed, but when the silsesquioxane was increased, the effect as a plasticizer Is thought to have appeared.

When a dynamic property test was conducted in the same manner as in Example 2, the shear modulus at a test temperature of 20° C. and a test frequency of 1 Hz was found to be the weight of trimethylsilylated polymethylsilsesquioxane and polydimethylsiloxane. 17MPa when the ratio is 20:80, 30MPa when the ratio is 40:60
The value was lower than that of the vinyldimethylsilylated polymethylsilsesquioxane described in Examples 2 and 3. The difference from the data of Examples 2 and 3 in the dynamic test is smaller than that in the static tensile test described above, because the deformation during the test is in the linear region, and thus cross-linking occurs between silsesquioxane and polydimethylsiloxane. It is probable that the absence was not reflected clearly.

[0052]

INDUSTRIAL APPLICABILITY According to the present invention, a specific polymethylsilsesquioxane is added to a polymer such as polydimethylsiloxane, and the polymethylsilsesquioxane is added to these polymers so that the addition effect can be obtained. It has a compatibility point and gives a reactive site capable of crosslinking with these polymers. This makes it possible to apply the polymethylsilsesquioxane in a wide range of applications such as a reinforcing filler for rubber. Furthermore, the reactive polymethylsilsesquioxane of the present invention enables curing by polyaddition or addition polymerization of the polymethylsilsesquioxane.

[Brief description of drawings]

1] [CH ₃ SiO _3/2 ] _n [CH in the present invention
₃ is a graph showing the range of m and n of polymethylsilsesquioxane represented by ₃ Si(OH)O _2/2 ] _m .

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[Procedure amendment]

[Submission date] February 16, 1998

[Procedure Amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0010

[Correction method] Change

[Correction content]

The polymethylsilsesquioxane used in the present invention has a polystyrene reduced number average molecular weight (Mn) of 38.
In the range of 0 to 2000 and having the formula [CH ₃ SiO _3/2 ] _n [CH ₃ Si(OH)O _2/2 ].
_m [m, n is a positive number giving the above molecular weight, m/(m+
The value of n) is in the area A of FIG. The region A is surrounded by each straight line represented by the following equations 1 to 4 in the graph of FIG. 1 in which the horizontal axis is 1/(Mn×10 ⁻³ ) and the vertical axis is m/(m+n). This is a region that is included in each line and includes the intersection of each line. (Formula 1): m/(m+n)=0.034/(Mn×10
^-3 )+ 0.10 (Formula 2): 1/(Mn×10 ^-3 )=1000/2000 (Formula 3): 1/(Mn×10 ^-3 )=1000/380 (Formula 4): m/ (M+n)=0.034/(Mn×10
^-3 )]]. The polymethylsilsesquioxane preferably contains an oxygen-containing organic solvent and, on the other hand, 50%
A methyltrihalosilane represented by the formula: MeSiX ₃ (Me is a methyl group, X is a halogen atom) in a two-phase system of water and an organic solvent containing or not containing a hydrocarbon solvent in an amount of less than or equal to volume%. It is produced by condensing hydrolysis and its hydrolysis product. If this production method is not used, the flexibility and heat resistance of the film of the cured product of this polymethylsilsesquioxane will be reduced even if the molecular weight and silanol group content are within the above ranges. That is, as described above, it does not become a characteristic polymethylsilsesquioxane.

Claims (8)

[Claims] 1. A polystyrene equivalent number average molecular weight (Mn).
Is in the range of 380 to 2000, and has the formula [CH ₃ SiO _3/2 ] _n [CH ₃ Si(OH)O _2/2 ].
_m [m, n is a positive number giving the above molecular weight, m/(m+
The value of n) is in the area A of FIG. The region A is surrounded by each straight line represented by the following equations 1 to 4 in the graph of FIG. 1 in which the horizontal axis is 1/(Mn×10 ⁻³ ) and the vertical axis is m/(m+n). This is a region that is included in each line and includes the intersection of each line. (Formula 1): m/(m+n)=0.152/Mn×1
0 ⁻³ )+0.10 (Formula 2): 1/(Mn×10 ⁻³ )=1000/2000 (Formula 3): 1/(Mn×10 ⁻³ )=1000/380 (Formula 4): m/ (M+n)=0.034/(Mn×10
^-3 )]], which is obtained by silylating a silanol group of polymethylsilsesquioxane represented by the formula: [CH ₃ SiO _3/2 ] _n [CH ₃ Si(OH)O _2/2 ].
_mk [CH ₃ Si(OSiR ¹ R ² R ³ )O _2/2 ] _k [In the above formula, k is a positive number smaller than m,
The amount of residual silanol groups represented by (m−k)/(m+n) is 0.12 or less, and R ¹ , R ² and R ³ are substituted or unsubstituted monovalent hydrocarbon groups, one of which is The above is a group having a crosslinkable carbon-carbon double bond]. 2. The polymethylsilsesquioxane according to claim 1, wherein the polymethylsilsesquioxane contains an oxygen-containing organic solvent, and contains 50% by volume or less of a hydrocarbon solvent or not, and an organic solvent and water. In the two-phase system, the formula: MeSiX ₃ (M
e is a methyl group and X is a halogen atom. The silylated polymethylsilsesquioxane according to claim 1, which is produced by hydrolyzing methyltrihalosilane represented by the formula (4) and condensing the hydrolysis product. 3. The silylated polymethylsilsesquioxane according to claim 1 or 2, wherein R ^{1 to} R ³ are one or more selected from the following combinations: (a) or (b). The silylated polymethylsilsesquioxane according to claim 1 or 2. (A) R ¹ =R ² =methyl group, R ³ =vinyl group (b) R ¹ =R ² =methyl group, R ³ =5-hexenyl group 4. A polystyrene equivalent number average molecular weight (Mn)
Is in the range of 380 to 2000, and has the formula [CH ₃ SiO _3/2 ] _n [CH ₃ Si(OH)O _2/2 ].
_m [m, n is a positive number giving the above molecular weight, m/(m+
The value of n) is in the area A of FIG. The region A is surrounded by each straight line represented by the following equations 1 to 4 in the graph of FIG. 1 in which the horizontal axis is 1/(Mn×10 ⁻³ ) and the vertical axis is m/(m+n). This is a region that is included in each line and includes the intersection of each line. (Formula 1): m/(m+n)=0.152/(Mn×10
^-3 )+0.10 (Formula 2): 1/(Mn×10 ^-3 )=1000/2000 (Formula 3): 1/(Mn×10 ^-3 )=1000/380 (Formula 4): m/( m+n)=0.034/Mn×1
0 ^-3 )], a silanol group of polymethylsilsesquioxane represented by the formula [CH ₃ SiO _3/2 ] _n [CH ₃ Si(OH)O _2/2 ]
_mk [CH ₃ Si(OSiR ¹ R ² R ³ )O _2/2 ] _k [In the above formula, k is a positive number smaller than m,
The amount of residual silanol groups represented by (m−k)/(m+n) is 0.12 or less, and R ¹ , R ² and R ³ are substituted or unsubstituted monovalent hydrocarbon groups, one of which is The above is a group having a crosslinkable carbon-carbon double bond], the method for producing a silylated polymethylsilsesquioxane. 5. The polymethylsilsesquioxane according to claim 4, which contains an oxygen-containing organic solvent, and contains or does not contain 50% by volume or less of a hydrocarbon solvent, and water. In the two-phase system, the formula: MeSiX ₃ (M
e is a methyl group and X is a halogen atom. The method for producing a silylated polymethylsilsesquioxane according to claim 4, which is produced by hydrolyzing methyltrihalosilane represented by the formula (4) and condensing a hydrolysis product thereof. 6. The silylated polymethylsilsesquioxane according to claim 4 or 5, wherein R ¹ , R ² and R ³ are at least one selected from the following combinations (a) and (b): The method for producing the silylated polymethylsilsesquioxane according to claim 4 or 5. (A) R ¹ =R ² =methyl group, R ³ =vinyl group (b) R ¹ =R ² =methyl group, R ³ =5-hexenyl group 7. A curable composition comprising the following components and: Component Silylated polymethylsilsesquioxane component according to claim 1, claim 2 or claim 3, a polysiloxane compound having an average of two or more hydrogen atoms directly bonded to Si atoms in one molecule Component, curing catalyst 8. The curable composition according to claim 7, wherein the curable composition further contains the following components. Ingredients Crosslinkable carbon-carbon double bonds average 2 per molecule.
Organopolysiloxane with more than one